Insecticide composition



Patented Feb. 13, 1945 Y 2,369,429 7 I INSECTICIDE COMPOSITION Clifford J. Boissonon, Concord, CaiiL, assignox' to 'Shell Development Company, San Francisco,

Oalii.'., a, corporation of Delaware No Drawing. Application June 30, 1942, Serial No. 449,156

9 Claims. 01. 167-42) This invention relates to a new and improved insecticidal liquid comprising a spray oil in water emulsion. -More particularly, it pertains to an additive for such a composition, which additive is an agent for improving the deposition of the spray oil from the aqueous emulsion as well as for improving the dispersity of the spray oil in the water.

Insecticidal compositions have long been used and'applied to foliage, fruit and/or plants as liquid or vapor sprays. The eiiectiveness of an insecticide spray depends upon the even distribution of the spray oil on and adherence of the spray oil to the object sprayed. In efi'ecting this distribution the spray oil is often dispersed in a liquid carrier such as Water. In actual practice much of the liquid carrier runs oil the foliage carrying with it considerable quantities of the spray oil which are thus lost. It is therefore important to minimize the carrying-oil" of the spray oil and to increase its deposition from the carrier liquid. Accordingly, if the deposition of the spray oil from the aqueous emulsion is increased, lower concentration of the spray oil may be used to obtain the same previous lethal effect. Hence a substantial economic saving is accomplished.

, A primary object of this invention is to produce an effective, practical and economical insecticidal composition. Another objectis to'provide an additive for insecticidal compositions capable of causing increased deposits and adherence of The mineral oil may act as the insecticide itself or specific repellents or insecticides may be added to it such as pyrethrum, rotenone, derris resins,

nicotine, aliphatic thiocyanates, nitrocresols, nitrophenols, cresyllc acids, alkyl amines, pine oils, halogenated hydrocarbons such as chloritoxic ingredients when they are sprayed in the storm or an aqueous emulsion'on foliage, fruits or dormant plants. A further object is to provide an additive which is not only a depositing agent but is also an emulsifying agent. thereby increasing the dispersity of the spray oil in its aqueous carrier. V

, The insecticidal composition of this invention comprises a spray oil containing the active material for repelling or killing harmful pests, a small amount of a depositing agent, and an aqueous carrier to aid in the distribution of saidactive material. In addition other ingredients may be'present, including emulsifying agents to disperse the spray oil in the aqueous carrier, de-

positing agents to aid the adherence of the spray oil to the object sprayed. anti-penetrants to prevent the spray oil from entering the pores and l. the plant on which it is sprayed, spread my agents to distribute the spray'oil over the tween about 40 and 70 seconds, and having an' unsulionated residue preferably above about 70%.

nated naphthalenes, etc.

The depositing agents of this invention comprise esters which are at least slightly soluble in both the spray oil and water. Suitable esters are carboxylic acid esters of triand tetra-hydroxy alcohols having a neo-carbon atom wherein at least one and preferably two or more of the hydroxy radicals are esterified. A nee-carbon atom is one that is attached directly to four other carbon atoms.

Alcohols containing a neo-carbon atom are represented by the formula:

enema a- (CH:),,OH

zomhon wherein :c, 1 and z are integers preferably one (1), and It is a hydrocarbon radical which may be aliphatic, alicyclic or aromatic and may comprise groups such as methyl, ethyl, propyl, isopropyl, butyl, amyl, hexyl and higher alkyl groups; cyclohexyl, methyl cyclohexyl, and-other alkyl cyclohexyl and diand poly-alicyclic radicells, such as may be obtained by hydrogenation of alkyl phenols, alkyl naphthols or of cyclic polymerization products of acetone, methyl ethyl ketone, mesityl oxide, etc.; phenyl, naphthyl and their alkyl derivatives, such as methyl phenyl, ethyl phenyl, methyl naphthyl, etc. The hydrocarbon radicals may contain preferably not more than one polar substitution group, in particular,

hydroxyl such as methanol, ethanol, pronanoi,

or nitrogen atom in a hve or six membered ring, such as fur-an, thiophene, pyridine, duinoline, etc.

A preferred group of such compounds are those in which R is a hydronyl substituted hydrocarbon I or carbinol group, such.

mcrnorm.

flfhese alcohols may be prepared by reacting hydrocarbon trihalogen oi. the general formula hr-c-if-lals with silver or potassium cyanides to form a nitrile R-C-(C:-:-N s, hydrogenating the nitrileto the e and converting the amine, to the corresponding alcohol by treating the" former wtih nitrous acid? Two alcohols, pentaerythritol and 2-=beta,beta',beta"-tertiary trihydrory butylpyridine are readily. and cheaply pre-,

pyridine aldehyde respectively with formaldehyde as in pentaerythritol q 2,2-dimethylol-butanol-1;

in the presence of lime. This reaction is however not applicable generally.

' Polyhydroxy alcohols of the above types are normally insoluble in mineral oils. It is therefore necessary to esterify these alcohols with carboxylic acids of suflicient carbon atoms to impart solubility in the spray oil. Acids suitable for this purpose are carboxylic acids having 7 or more carbon .atoms per molecule," and preferably between 12 and 24 carbon atoms. These acids may be saturated or unsaturated aliphatic or cycloaliphatic carboxylic acids preferably having not more thanone olefinic double bond, such as wool fats and fatty acids, e. g., lauric, myristic, palmitic, stearic, arachidic, eicosane-carboxylic, behenic, oleic, erucic, etc.; petroleum naphthenic acids; aromatic acids such as alkyl benzoic, alkyl benzyl acetic, phenyl acetic, phenyl stearic, alkyl pyridine carboxylic acids, etc. The saturated fatty acids are preferred in general.

Some specific examples of the esters derived I from the above-mentioned alcohols and acids which may be employed as depositing agents are penta-erythritol distearate, penta-erythritol tetrastearate, and diand tri-fatty acid esters of 2'-methyl,2-methylol propane-1,3-diol; 2-chloromethyl,2-methylo1-propane-1,3-diol; 3-methyl- 2 nitro,2 'methylo1 propane- 1,3-diol; 2-beta,beta',beta' -trihydroxytertiary butyl pyridine; and 2,2'-dim'ethylol-3-- hydroxy normal propyl benzene.

The amount of such esters necessary to be effective inan insecticidal composition usually ranges from about .01% to 2% by volume of the insecticidal material therein. However, this amount may vary somewhat depending upon the act as emulsifying agents, it is not always necessary to add these additional emulsifying agents to effect proper dispersion.

In order to save shipping cost the insecticide composition is usually shippedto place of use without the aqueous carrier, the latter being added in the field. Emulsification may-be eifected by any conventional means of agitation ineluding circulation through the spraying machine particular ester chosen and its relation to theother ingredients of the insecticidal composition, sometimes being larger or smaller than the abcve mentioned range. A preferred amount for several specific depositing agents has been found to be between about .2% and 1.0% by volume.

These esters may be'added to either the spray oil or to the water used in making up the composition, whichever isthe more convenient. It is preferable,-however, to add them to the spray oil.

It is often desirable to employ a mutual solvent for the depositing agent and the spray oil in order to facilitate dispersion of the depositing agent in the insecticidal composition. Some such mutual solvents are phenol; alkyl phenols such as cresylic acid; certain ethers, particularly cellosolves and carbitols like monoand di-ethylene glycol monobutyl ethers; alcohols such as butanols, pentanols, hexanols, cyclohexanol; ketones such as methyl ethyl ketone, di-isopropyl ketone, di-isobutyl ketone; etc. Amounts less than 5% by volume are normally sufficient, but less than 1% by volume being preferred if sufficient, because relatively large quantities tend to break the emulsion of the spray oiland water.

. the orifice for a period of, 6 seconds.

in the field. The amount of water employed varies depending upon whether the insecticidal composition is to be used as a summer spray for foliage, or as a winter dormant spray. In a summer spray the amount of water usually varies between 96% and 99% by volume of the insecticidal composition, while in a dormant sprayas little as 94% water may be used.

The insecticidal composition of this invention which contains the particular depositing and" emulsifying agent described herein may also contain other additives such as anti-penetrants like aluminum naphthenate and Visco resins in the oil phase, as well as spreading agents in the oil or water phase such as blood, albumen, lecithin, and/or other known depositing agents.

The following examples demonstrate the efiectiveness of the depositing agents of this invention. Five samples of insecticidal compositions were prepared, one of which contained no depositing agents and was used as a standard. The spray oil employed in each was a light medium mineral oil having a Saybolt Universal viscosity at I00 F.

of 68 seconds and an unsulfonatedresidue of 92%. Water emulsions were produced with each sample containing 1.67% by volume of the oil.

The emulsification was effected by circulating the sample through a small field-type spraying machine under a pressure of 500 lbs. per sq. in. for a period of 30 seconds. This emulsion was then sprayed at this pressure through a nozzle having an orifice diameter of inch on to a rotating four-ounce sample bottle 6 feet away from The Sam,- ple bottle had been previously coated with beeswax to simulate the surface of fruit and foliage and accurately weighed. After spraying, the bottles were dried in a current of. dust-free dye air to evaporate all the water thereon and then weighed.

Each sample was sprayed on to three bottles and the average differences. in weights before and after spraying were then calculated to the nearest microgram. The ratio between the weight deposited for each sample andthe weight deposited by the standard sample containing no depositing agent gives the depositing factor.

From the table below it can be seen that as little If a stable dispersion of the spray oil in water is desired, the addition of further emulsifying agents may be required, such as alkyl sulfonates' and sulfates, including-oil-soluble sodium, potasisium or ammonium salts of petroleum sulfonic,

acids; fatty and naphthenic acid soaps; polymerized animal and vegetable .oils; non-ionic emulsifiers such as vegetable and animal wages and tallows. It is necessary that these emulsifying agents do not 'react with the ingredients in the insecticidal material. However, since the particular depositing agents of this invention also as .5% of the depositing agent of I this invention per volume of the spray oil more than doubles the amount of its deposit.

Peggent o eg}: 5 Depositing posilhgg ggf gg g gg spray oll ggfi g' per m1. factor oioil 1 (standard). None None None 1 2 Penta-erythritol .5 do 2.84

- distearate. 3 .d o 1.0 ...do 2.46 4 Penta-erythritol 1.0 do 2.11

tetrastearate. 8 Penta-erythritol .5 .OGrotenone. 8

- distearate. I

In the above samples no additional emulsifying agent was added to the spray oil and the emulsion was obtained by the emulsifying prop-.

erties of the depositing agent employed.

I claim as my invention: 1. An insecticidal composition for use in aqueous emulsions comprising spray oil, and between about .01 and 2% by volume of said spray oil of .a depositing and emulsifying agent consisting of a carboxylic acid ester of a polyhydroxy alcohol containing at least 3 and not-more than 4 hydroxy radicals and having a neo carbon atom, said alcohol being esterified with an acid having 7 or more carbon atoms per molecule.

2. The composition of claim 2 wherein the depositing and emulsifying agent is a carboxylic acid ester of penta-erythritol.

3. An insecticidal composition comprising an insecticide, a mineral spray oil, an aqueous carrier for said insecticide and said oil, and between about .01 and 2% by volume of said oil of a depositing agent consisting of an ester'of a polyhydroxy alcohol containing at least 3 and not more than 4 hydroxy radicals and having a neo carbon atom, said alcohol being esterified with an acid having between 12 and 24 carbon atoms per molecule.

- 4. The composition of claim 3 wherein the depositing and emulsifying agent is penta-erythritol distearate.

5. The composition of claim 3 wherein the depositing and emulsifying agent is penta-erythritol tetrastearate.

6. The composition of claim 3 wherein the depositing and emulsifying agent is penta-erythritol distearate and the percent thereof is between about .1 and about 1.0 by volume of said mineral spray oil. a

7. An insecticidal composition, a spray oil, an aqueous carrier therefor, and about .01 to 2% by volume based on the spray oil of a depositing agent consisting of a carboxylic acid ester of an alcohol having a neo carbon atom and being of the general formula:

( I) a H wherein m, y and z are integers and R is an or-' ganic radical selected from the class consisting of aliphatic, alicyclic, aromatic, and heterocyclic compounds of an aromatic nature, said esterifying acid having at least 7 carbon atoms.

8. A method of increasing the deposition of spray oil on plants from a mixture containin it and an aqueous carrier therefor comprising adding to said spray oil about .01 to 2% by "volume of a depositing agent consisting of a carboxylic acid ester of a polyl'iydroxy alcohol having a neo carbon atom and containing at least 3 and not more than 4 hydroxy radicals, saidalcohol being esterified with an acid having 7 or more carbon atoms per molecule, and spraying said mixture on plants.

9. A method of increasing the deposition of spray oil on plants from a mixture containing it and an aqueous carrier therefor comprising adding to said spray oil about .01 to 2%'by volume of a depositing and emulsifying a ent consisting of a fatty acid ester of penta-erythritol,

which latter is esterified with an acid having between 12 and 24 carbon atoms per molecule, and spraying said mixture on plants.

Y CLIFFORD J. BOISSONOU.

CERTIFICATE OF CORRECTION. Patent No. 2,569,LL29. February 15, 19145.

- CLIFFORD J. BoIssoNoU.

It is hereby certified that error appears in the 'printed specification of the above nuinbered patent requiring correction as follows: Page 5, first column, line 15, for the claim reference numeral "2" read -l-; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 6th day of November, A. D. 19L 5.

Leslie Frazer First Assistant Commissioner of Patents. 

